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E-raamat: Chirality at Solid Surfaces

Stephen J. Jenkins

Formaat: EPUB+DRM
Ilmumisaeg: 08-Jan-2018
Kirjastus: John Wiley & Sons Inc
Keel: eng
ISBN-13: 9781118880142

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Surface chemistry & adsorption

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Formaat: EPUB+DRM
Ilmumisaeg: 08-Jan-2018
Kirjastus: John Wiley & Sons Inc
Keel: eng
ISBN-13: 9781118880142

Teised raamatud teemal:

Surface chemistry & adsorption

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A comprehensive introduction to the fundamental aspects of surface chirality, covering both chemical and physical consequences

Written by a leading expert in the field, Chirality at Solid Surfaces offers an introduction to the concept of chirality at surfaces, starting from the foundation of chirality in isolated molecules and bulk systems. Fundamental properties such as surface energy and surface stress are then linked to a universal systematization of surface structure and symmetry. The author includes key examples of surface chemistry and physics, such as the interplay between adsorbate and substrate chirality, amplification of chirality, chiral catalysis, and the influence of surface chirality upon optical and magnetic phenomena. The book also explores the chirality apparent in the electronic structure of graphene, topological insulators and half-metallic materials.

This important reference:

Provides an introduction to the fundamental concept of chirality
Contains discussions of the chemical and physical consequences of surface chirality, including magnetic, electronic and optical properties in addition to molecular properties
Offers an account of the most current research needed to support growth in the field

Written for surface scientists, professionals in the field, academics, and students, Chirality at Solid Surfaces is an essential resource that contains an overview of the fundamentals of surface chirality and reviews both the chemical and physical consequences.

Preface

xiii

Acknowledgements

xxiii

1 Fundamentals of Chirality

(20)

1.1 Point and Space Groups

(2)

1.2 Proper and Improper Symmetry

(1)

1.3 Chirality in Finitude and Infinity

(4)

1.3.1 Molecular Chirality

(3)

1.3.2 Crystalline Chirality

(1)

1.4 Routes to Surface Chirality

(5)

1.4.1 Surfaces of Intrinsically Chiral Crystals

(1)

1.4.2 Intrinsically Chiral Surfaces of Achiral Crystals

(1)

1.4.3 Chiral Modification of Achiral Surfaces

(3)

1.5 Diastereoisomerism Defined

(1)

1.6 Quantifying Chirality?

(2)

1.7 Enantiomeric Excess

(2)

1.8 Synthesis, Separation and Sensing

(2)

References

(1)

2 Surface Symmetry and Structure

(44)

2.1 Spherical Representation of Symmetry

(3)

2.2 Spherical Representation of Structure

(3)

2.3 Stereographic Projections: Flattening the Globe

(2)

2.4 Surfaces of the Face-Centred Cubic Structure

(7)

2.4.1 Reconciliation of Symmetry and Primary Structure

(3)

2.4.2 Secondary and Tertiary Structure

(2)

2.4.3 Commentary

(2)

2.5 Surfaces of the Body-Centred Cubic Structure

(6)

2.5.1 Reconciliation of Symmetry and Primary Structure

(2)

2.5.2 Secondary and Tertiary Structure

(1)

2.5.3 Commentary

(2)

2.6 Surfaces of the Hexagonal Close-Packed Structure

(14)

2.6.1 Symmetry

(5)

2.6.2 Primary Structure

(4)

2.6.3 Reconciliation of Symmetry and Primary Structure

(3)

2.6.4 Commentary

(1)

2.7 Surfaces of the Diamond Structure

(9)

2.7.1 Symmetry

(2)

2.7.2 Primary Structure

(1)

2.7.3 Reconciliation of Symmetry and Primary Structure

(3)

2.7.4 Commentary

(1)

References

(2)

3 Surface Energy and Surface Stress

(28)

3.1 Thermodynamic Definition of Surface Energy

(5)

3.2 The Tensor Nature of Surface Stress

(1)

3.3 Visualisations of Surface Stress: Iconic Conics

(4)

3.3.1 The Normal Stress Conic

(1)

3.3.2 The Shear Stress Quartic

(1)

3.3.3 The Stress Ellipse

(1)

3.4 Symmetry of the Surface Stress: Eccentricity and Orientation

(6)

3.4.1 Stereography and Surface Stress

(2)

3.4.2 Racemic Surface Stress

(1)

3.4.3 Adsorbate-Induced Asymmetry in Surface Stress

(1)

3.5 Measurement of Differential Surface Stress

(5)

3.5.1 Island Shape Measurement

(1)

3.5.2 Contact Angle Measurement

(3)

3.5.3 Cantilever Deformation

(1)

3.6 Facet Formation and the Wulff Construction

(7)

3.6.1 Ridge-and-Furrow Facets

(2)

3.6.2 Pyramid-and-Pit Facets

(1)

3.6.3 Geometrical Construction

(2)

References

(2)

4 Asymmetric Adsorption on Achiral Substrates

(72)

4.1 Achiral Adsorbates: Gliding Through Broken Mirrors

(4)

4.2 Prochiral Adsorbates: Chirality in Context

(15)

4.2.1 Guanine on Au{111}

(3)

4.2.2 Stilbene Derivatives on Cu{100} and Cu{110}

101

(1)

4.2.3 Glycine on Cu{110} and Cu{311}

102

(5)

4.2.4 Succinic and Fumaric Acids on Cu{110}

107

(4)

4.2.5 Meso-Tartaric Acid on Cu{110}

111

(1)

4.3 Chiral Adsorbates: Act Locally, Think Globally

112

(37)

4.3.1 Alanine on Cu{110} and Cu{311}

112

(8)

4.3.2 Proline on Cu{110} and Cu{311}

120

(5)

4.3.3 Serine and Lysine on Cu{110}

125

(3)

4.3.4 Cysteine on Cu{110} and Au{110}

128

(7)

4.3.5 Tartaric Acid on Cu{110}

135

(5)

4.3.6 Glutamic Acid on Ag{110} and Ag{100}

140

(5)

4.3.7 2-Butanolon Au{111}

145

(1)

4.3.8 Tartaric Acid on Ni{111}

146

(1)

4.3.9 Alanine on Pd{111}

147

(2)

4.4 Chiral Facetting: Remodelling the Surface

149

(2)

4.4.1 Glycine, Alanine and Lysine on Cu{100}

150

(1)

4.5 Chiral Metallorganic Frameworks: Into the Second Dimension

151

(5)

4.5.1 Glutamic Acid on Ni/Au{111}

152

(1)

4.5.2 Lysine on Ni/Au{111}

153

(1)

4.5.3 Proline on Ni/Au{111}

154

(2)

4.6 Executive Summary

156

(9)

References

159

(6)

5 Asymmetric Adsorption on Chiral Substrates

165

(32)

5.1 Achiral Adsorbates on Intrinsically Chiral Substrates: Fault-Lines and Facets

165

(3)

5.1.1 Oxygen on Cu{531}

165

(2)

5.1.2 Cyclohexanone on Cu{643}

167

(1)

5.1.3 NaCl on Cu{532}

168

(1)

5.2 Prochiral Adsorbates on Intrinsically Chiral Substrates: Familiar and Strange

168

(3)

5.2.1 Glycine on Cu{531}

169

(2)

5.3 Chiral Adsorbates on Intrinsically Chiral Substrates: Diastereomeric Effects

171

(13)

5.3.1 Alanine on Cu{531}

171

(2)

5.3.2 Serine on Cu{531}

173

(1)

5.3.3 Cysteine on Cu{531} and Au{17 11 9}

174

(2)

5.3.4 Tartaric Acid on Cu{531}

176

(1)

5.3.5 Propylene Oxide and 3-Methylcyclohexanone on Cu{643}

176

(4)

5.3.6 3-Methylcyclohexanone on Cu{531}, Cu{651} and Cu{13 9 1}

180

(2)

5.3.7 Alanine, Serine, Lysine, Phenylalanine and Aspartic Acid on Cu{3 1 17}

182

(2)

5.4 Chiral Adsorbates on Chirally Modified Substrates: Diastereomeric Effects II

184

(7)

5.4.1 Propylene Oxide on 2-Butanol-Modified Pd{111} and Pt{111}

185

(3)

5.4.2 Propylene Oxide on 2-Methylbutanoic Acid-Modified Pd{111} and Pt{111}

188

(1)

5.4.3 Propylene Oxide on Amino Acid-Modified Pd{111}

189

(1)

5.4.4 Glycidol on Tartaric Acid-Modified Pd{111}

190

(1)

5.4.5 Propylene Oxide on Lysine-Modified Cu{100}

191

(1)

5.5 Executive Summary

191

(2)

References

193

(4)

6 Chiral Amplification

197

(28)

6.1 Kinetic Amplification: Surface Explosions

197

(9)

6.1.1 Tartaric and Malic Acids on Cu{110}

200

(2)

6.1.2 Tartaric Acid on Cu{643}, Cu{17 5 1}, Cu{531} and Cu{651}

202

(4)

6.2 Thermodynamic Amplification: Sergeants, Soldiers and Majority Rule

206

(19)

6.2.1 Tartaric, Succinic and Malic Acids on Cu{110}

206

(4)

6.2.2 Heptahelicene on Cu{111}, Ag{111} and Au{111}

210

(5)

6.2.3 Aspartic Acid on Cu{111}

215

(2)

6.2.4 Supramolecular Assemblies on Highly Ordered Pyrolytic Graphite

217

(5)

References

222

(3)

7 Asymmetric Heterogeneous Catalysis

225

(32)

7.1 Electro-Oxidation of Glucose on Pt{643} and Pt{321}

227

(8)

7.2 Electron-Stimulated Oxidation of Methyl Lactate on Cu{643}

235

(1)

7.3 Hydrogenation of α-Ketoesters over Platinum: The Orito Reaction

236

(11)

7.3.1 Adsorption Geometry of Methyl and Ethyl Pyruvate

237

(3)

7.3.2 Adsorption Geometry of Cinchonidine and its Cousins

240

(4)

7.3.3 Binding and Reaction in the Chiral Complex

244

(3)

7.4 Hydrogenation of β-Ketoesters over Nickel: The Izumi Reaction

247

(10)

7.4.1 Adsorption Geometry of Methyl Acetoacetate

247

(1)

7.4.2 Two-Dimensional Cocrystallisation: Tartaric/Glutamic Acid Modification

248

(2)

7.4.3 Defect-Localised Oligomerisation: Modification by Aspartic Acid

250

(3)

References

253

(4)

8 Optical Consequences of Surface Chirality

257

(22)

8.1 The Nature of Light

258

(1)

8.2 Planar and Twisted Light

258

(4)

8.2.1 Linear and Circular Polarisation

259

(2)

8.2.2 Polarisation on a Helix

261

(1)

8.3 Dichroic Photoemission

262

(5)

8.4 Non-linear Optics in Chiral Systems

267

(9)

8.4.1 Symmetry Constraints on Non-linear Optical Phenomena

267

(5)

8.4.2 Implications for Chiral Surfaces

272

(1)

8.4.3 Chiral SHG on Cu{111} and Au{110}

273

(3)

8.5 Near-Field Phenomena

276

(3)

References

277

(2)

9 Magnetic Consequences of Surface Chirality

279

(36)

9.1 Spin and Orbital Magnetism

279

(6)

9.1.1 Fermions and the Dirac Equation

280

(3)

9.1.2 Spin-Orbit Coupling

283

(2)

9.2 Bulk Magnetocrystalline Anisotropy

285

(10)

9.2.1 Laue Class Oh (Cubic Crystal System: Oh, Td and O)

287

(1)

9.2.2 Laue Class Th (Cubic Crystal system: Th and T)

287

(1)

9.2.3 Laue Class D6h (Hexagonal Crystal System: D6h, D3h, C6v and D6)

287

(1)

9.2.4 Laue Class C6h (Hexagonal Crystal System: C6h, C3h and C6)

288

(1)

9.2.5 Laue Class D3d (Trigonal Crystal System: D3d, C3v and D3)

288

(1)

9.2.6 Laue Class S6 (Trigonal Crystal System: S6 and C3)

289

(1)

9.2.7 Laue Class D4h (Tetragonal Crystal System: D4h, D2d, C4v and D4)

289

(1)

9.2.8 Laue Class C4h (Tetragonal Crystal System: C4h, S4, & C4)

290

(1)

9.2.9 Laue Class D2h (Orthorhombic Crystal System: D2h, C2v, and D2)

290

(2)

9.2.10 Laue Class C2h (Monoclinic Crystal System: C2h, C1h, and C2)

292

(1)

9.2.11 Laue Class S2 (Triclinic Crystal System: S2 and C1)

293

(1)

9.2.12 General Comments

294

(1)

9.3 Surface Magnetocrystalline Anisotropy

295

(4)

9.3.1 Surface MCA of Face-Centred and Body-Centred Cubic Ferromagnets

296

(2)

9.3.2 Role of Adsorbates and Reconstruction

298

(1)

9.4 An Aside: Vectors and Pseudovectors

299

(2)

9.5 Spin Waves in Centrosymmetric Media

301

(3)

9.5.1 Spin Helices

301

(2)

9.5.2 Spin Spirals

303

(1)

9.6 Spin Waves at a Featureless Surface

304

(2)

9.6.1 Spin Helices

304

(1)

9.6.2 Spin Spirals

305

(1)

9.7 Spin Waves at Structured Surfaces

306

(1)

9.7.1 Spin Helices at Achiral Surfaces

306

(1)

9.7.2 Spin Helices at Chiral Surfaces

307

(1)

9.7.3 Spin Spirals at Achiral Surfaces

307

(1)

9.7 A Spin Spirals at Chiral Surfaces

307

(1)

9.8 Surface Spin Spirals Observed

308

(1)

9.9 Skyrmions, or How to Brush a Hedgehog

309

(6)

References

313

(2)

10 Chiral Electronic States in Two Dimensions

315

(16)

10.1 Dirac Cones in Graphene

316

(5)

10.2 Dirac Cones at Half-Metal Surfaces

321

(2)

10.3 Dirac Cones at the Surfaces of Topological Insulators

323

(5)

10.4 Prospects for Electronic Chirality in the Chemical Context

328

(3)

References

329

(2)

11 Postscript

331

(4)

A List of Abbreviations

335

(2)

B Rules for Overlayer Periodicity Assignment

337

(8)

B.1 Substrate Lattice

337

(1)

B.2 Overlayer Lattice

338

(1)

B.3 Illustrative Examples

339

(6)

References

343

(2)

C Further Reading

345

(2)

Index

347

Dr. Stephen J. Jenkins, leads the Surface Science group in the Department of Chemistry at Cambridge University, where he directs both experimental and computational research on the physical and chemical properties of metal surfaces. His broad interest in the complexities of intermolecular interactions at surfaces finds particular focus in the expression of chirality in two dimensions, and its implications for asymmetric chemistry. He has worked in surface science for the past twenty-five years, and has published over 140 papers on a variety of topics within that field.

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